As a subclass of commercially available polymers, polyurethane elastomers have several properties whose advantages confer unique benefits on these products. Typically, polyurethanes show high abrasion resistance with high load bearing, excellent cut and tear resistance, high hardness, resistance to ozone degradation, yet are pourable and castable. Compared to metals, polyurethanes are lighter in weight, less noisy in use, show better wear and excellent corrosion resistance while being capable of cheap fabrication. Compared to other plastics, polyurethanes are non-brittle, much more resistant to abrasion, and exhibit good elastomeric memory. Polyurethanes find use in such diverse products as aircraft hitches, bushings, cams, gaskets, gravure rolls, star wheels, washers, scraper blades, impellers, gears, and drive wheels.
Part of the utility of polyurethanes derives from their enormous diversity of properties resulting from a relatively limited number of reactants. Typically, polyurethanes are prepared on site by curing urethane prepolymers, which are adducts of polyisocyanates and polyhydric alcohols. A large class of such prepolymers are approximately 2:1 adducts of a diisocyanate, OCN--Y--NCO, and a diol, HO--Z--OH, whose resulting structure is OCN--Y--NHCO.sub.2 --Z--O.sub.2 CNH--Y--NCO. Although Y is susceptible of great variety, usually being a divalent alkyl, cyclohexyl, or aromatic radical, in fact the most available prepolymers are made from toluene diisocyanate (TDI), most readily available as a mixture of 2,4- and 2,6-isomers which is rich in the former isomer, or methylene-4,4'-diphenylisocyanate (MDI). The diols used display a greater range of variety; Z may be a divalent alkyl radical (i.e., an alkylene group), and the diols frequently are ethers or esters which are the condensation products of glycols with alkylene oxides or dicarboxylic acids, resp.
The polyurethane elastomers are formed by curing the prepolymer. Curing is the reaction of the terminal isocyanate groups of the prepolymer with active hydrogens of a polyfunctional compound so as to form high polymers through chain extension and, in some cases, crosslinking. Diols, especially alkylene diols, are the most common curing agents for MDI-based prepolymers, and representing such diols with the structure HO--X--OH, where X is an organic moiety, most usually an alkylene group, the resulting polymer has as its repeating unit, EQU (--Y--NHCO.sub.2 ZO.sub.2 CNH--Y--NHCO.sub.2 --X--O--CONH--).
Where a triol or a higher polyhydric alcohol is used crosslinking occurs to afford a nonlinear polymer.
Although other polyfunctional chemicals, especially diamines, are theoretically suitable, with but a few exceptions none have achieved commercial importance as a curing agent. The major exception is 4,4'-methylene-di-ortho-chloroaniline, usually referred to as MOCA, a curing agent which is both a chain extender and a crosslinker. TDI-based prepolymers typically are cured with MOCA, and the resulting products account for perhaps most of the polyurethane elastomer market. One reason that polyhydric alcohols generally have gained acceptance as curing agents is that their reaction with urethane prepolymers is sufficiently fast to be convenient, but not so fast as to make it difficult to work with the resulting polymer. In casting polymers it is desirable that the set-up time be reasonably short, yet long enough for the material to be cast into molds. This property is conventionally referred to as pot life. Generally speaking, diamines react with prepolymers, and especially MDI-based prepolymers, so quickly that they are not usable as curing agents. However, primary aromatic diamines with electronegative groups on the aromatic ring, or with alkyl groups ortho to the amino moiety, exhibit sufficiently decreased reactivities with some prepolymers as to afford a desirable pot life, hence the use of, for example, MOCA as a curing agent for TDI-based prepolymers. However, MOCA and other of the aforementioned diamines still remain too reactive to be used, for example, with MDI-based prepolymers.
Although only primary aromatic diamines seem to have been investigated heretofore as curing agents, recently it was discovered that certain N,N'-dialkyl-4,4'-methylenedianilines are generally effective curing agents for a broad range of urethane prepolymers. See U.S. Pat. No. 4,578,446. The resulting polyurethanes often have the advantage of being thermoplastic rather than thermosetting, thereby making them especially useful as coatings, adhesives, and sealants. The secondary aromatic diamines of that invention had commercially acceptable pot lives as curing agents for many prepolymers, and afforded products with an impressive variety of properties.
The use of chain extenders, such as are the secondary aromatic diamines of the aforementioned invention, often leads to thermoplasticity, whereas the use of crosslinkers often leads to increased rigidity and lower compression set as well as a higher glass transition temperature and less swelling in solvents. It occurred to us that the use of aromatic polyamines, especially those that are extensively polyalkylated so as to be predominantly secondary aromatic polyamines, would be particularly advantageous curing agents, because the presence of more than two amino groups within the molecule would lead to crosslinking superimposed on chain extension. In fact, we have demonstrated this to be the case. In particular, we have found a large class of alkylated aromatic polyamines, which can be viewed as polymers whose repeating unit is x-amino-y-methylenephenyl, are excellent curing agents for urethane prepolymers. Among the advantages of the curing agents of this invention are that the resulting polyurethanes show excellent compression set, have quite high tensile strength, show a substantially higher glass transition temperature than usual with good solvent resistance. The resulting polyurethanes are thermosetting polymers, and also have the advantage that their properties remain relatively unchanged within a wide range of stoichiometry of curing agent and prepolymer. Therefore, the curing agents of this invention are very tolerant to mixing error, which is a decided manufacturing advantage. Additionally, the curing agents themselves for the most part are viscous liquids, rather than being powders, an advantage in their handling. The curing agents may be used for both TDI and MDI prepolymers, which are the two largest class of urethane prepolymers, show a good pot life and have excellent thermostability. In short, the unique properties of both the curing agents and the resulting polyurethanes make each very highly desirable.